Abrasive material

ABSTRACT

An object of the present invention is to provide a polishing body, wherein the abrasive in the polishing body are extremely dispersed well, which provides stable polishing performance in the polishing process, and which can effectively reduce the occurrence of scratches even in a case a large quantity of the abrasive are contained. A polishing part constituting the polishing body in the invention is produced obtained by loading predetermined amounts of butadiene, styrene, methyl methacrylate, itaconic acid, acrylic acid, α-methylstyrenedimer, and t-dodecylmercaptan in an autoclave, making the mixture react for 16 hours at 75° C. to obtain an emulsion wherein a copolymer is dispersed, adjusting this emulsion to pH8.5, incorporating cerium oxide powder with an average primary particle diameter of 0.3 μm and stirring to obtain an aqueous dispersion, drying this aqueous dispersion by spreading it thinly across a film, and mold pressing the dried product obtained. The above-mentioned polishing part may have a crosslinked structure. The polishing body in the invention can be used favorably in a polishing pad and the like, for polishing the surface of a semiconductor wafer or the like.

FIELD OF THE ART

This invention relates to a polishing body, and to be more specific,relates to a polishing body wherein abrasive in the polishing body areextremely dispersed well. The polishing body in the invention can beused favorably as a polishing pad and the like for the polishing of thesurfaces of semiconductor wafers and the like.

BACKGROUND ART

Chemical mechanical polishing, also referred to as CMP, has beenconventionally used for polishing the surfaces of semiconductor wafersand the like. In CMP, polishing is performed by sliding while pressing asurface to be polished of the wafer and the like against a disk-likepolishing pad and at the same time, pouring a slurry (aqueousdispersion) wherein abrasive is dispersed, onto the polishing pad.However, it is difficult to supply the slurry, which is poured fromabove, between the surface to be polished and the polishing surface ofthe polishing pad, which are pressed against each other at highpressure, and it is said that the actual amount of functioning polishingagent is less than 1% of the total amount supplied. Moreover, thisslurry is expensive and furthermore, vast costs are required for thetreatment of used slurry.

Polishing body and the like that contain abrasive have been disclosed inJapanese Unexamined Patent Publication No. Hei-5-222356, JapaneseUnexamined Patent Publication No. Hei-8-294869, Japanese UnexaminedPatent Publication No. Hei-10-329032, Japanese Unexamined PatentPublication No. Hei-11-151659, Japanese Unexamined Patent PublicationNo. Hei-11-188647 and the like. However, with all of these cases,adequate prevention of scratching on the surface to be polished isconsidered to be difficult to achieve.

DISCLOSURE OF THE INVENTION

The present invention solves the above problems. And it is intended toprovide a polishing body wherein abrasive is extremely dispersed well,which provides stable polishing performance in the polishing process,and which can effectively reduce the occurrence of scratches on thesurface to be polished.

The present invention attains the object described above and can bedescribed as follows.

-   1. A polishing body having a polishing part that is formed by    solidifying an aqueous dispersion wherein a matrix material and    abrasive are dispersed and contained respectively.-   2. The polishing body according to 1 above, wherein the polishing    body is used for the polishing of semiconductors.

The above-mentioned polishing part may be one obtained by drying theabove-mentioned aqueous dispersion and forming the dried product. Theabove-mentioned aqueous dispersion may be one obtained by dispersingabrasive in an emulsion in which a matrix material is dispersed. Theabove-mentioned dried product may be obtained by spray drying of theabove-mentioned aqueous dispersion. The above-mentioned polishing partmay be a plate-like part and a supporting part may be laminated onto onesurface of the polishing part.

-   3. A polishing body having a polishing part that is formed by    solidifying an aqueous dispersion containing dispersed composite    particles wherein abrasive is attached to a matrix material.-   4. The polishing body according to 3 above, further a matrix    material and/or abrasive are dispersed and contained in the    above-mentioned aqueous dispersion.-   5. The polishing body according to 3 above, wherein the respective    zeta potentials of the above-mentioned matrix material and the    above-mentioned abrasive are opposite in sign and the difference of    the above-mentioned zeta potentials is 5 mV or more.-   6. The polishing body according to 3 above, wherein the polishing    body is used for the polishing of semiconductors.

The above-mentioned polishing part may be one obtained by drying theabove-mentioned aqueous dispersion and forming the dried product. Theabove-mentioned aqueous dispersion may be one obtained by dispersingabrasive in an emulsion in which a matrix material is dispersed. Theabove-mentioned dried product may be obtained by spray drying of theabove-mentioned aqueous dispersion. The above-mentioned polishing partmay be a plate-like part and a supporting part may be laminated onto onesurface of the polishing part.

-   7. A polishing body having a polishing part that is formed by    solidifying an aqueous dispersion wherein a matrix material    comprised of a crosslinkable polymer and abrasive are dispersed and    contained respectively, and a polishing part that has a crosslinked    structure.-   8. The polishing body according to 7 above, wherein the polishing    body is used for the polishing of semiconductors.

The above-mentioned polishing part may be one obtained by drying theabove-mentioned aqueous dispersion and forming the dried product. Theabove-mentioned aqueous dispersion may be one obtained by dispersingabrasive in an emulsion in which a matrix material is dispersed. Theabove-mentioned dried product may be obtained by spray drying of theabove-mentioned aqueous dispersion. The above-mentioned polishing partmay be a plate-like part and a supporting part may be laminated onto onesurface of the polishing part.

-   9. A polishing body having a polishing part that is formed by    solidifying an aqueous dispersion containing dispersed composite    particles wherein abrasive is attached to a matrix material    comprised of a crosslinkable polymer, and a polishing part that has    a crosslinked structure.-   10. The polishing body according to 9 above, wherein the respective    zeta potentials of the above-mentioned matrix material and the    above-mentioned abrasive are opposite in sign and the difference of    the above-mentioned zeta potentials is 5 mV or more.-   11. The polishing body according to 9 above, wherein the polishing    body is used for the polishing of semiconductors.

The above-mentioned polishing part may be one obtained by drying theabove-mentioned aqueous dispersion and forming the dried product. Theabove-mentioned aqueous dispersion may be dispersed and contained amatrix material and/or abrasive therein. The above-mentioned aqueousdispersion may be one obtained by dispersing abrasive in an emulsion inwhich a matrix material is dispersed. The above-mentioned dried productmay be obtained by spray drying of the above-mentioned aqueousdispersion. The above-mentioned polishing part may be a plate-like partand a supporting part may be laminated onto one surface of the polishingpart.

According to the polishing body in the invention, since abrasive isextremely dispersed well even in the case where a large amount ofabrasive is contained, the polishing performance is stable and theoccurrence of scratches can be reduced effectively.

In another mode of the invention, the polishing body that has apolishing part having a crosslinked structure shows excellent removalrate even with a cutting product since deterioration of the polishingbody due to heat during a cutting process is not likely to occur. Thusthis polishing body makes processing of a required small distribution ofthickness and cutting such as grooving easier without lowering thepolishing performance.

Furthermore according to the polishing body in another mode of theinvention, the particle size distribution of a powder that is a granularproduct produced by spray drying, can be made narrow and uniform. Thefilled amount in a mold in the process of powder molding is thus madestable, thereby reducing the distribution of the weights of individualmolded products, denseness distribution within a polishing body may bereduced, and a stable polishing performance for each polishing processwill be obtained.

The present invention will now be described in more detail.

A polishing body in the invention is characterized in having a polishingpart that is formed by solidifying an aqueous dispersion wherein amatrix material and abrasive are dispersed and contained respectively.

A polishing body in another mode of invention is characterized in havinga polishing part formed by solidifying an aqueous dispersion containingdispersed composite particles wherein abrasive is attached to a matrixmaterial. This aqueous dispersion containing composite particles mayfurthermore have a matrix material and/or abrasive dispersed andcontained therein.

That is, the polishing body in the invention is formed by solidifyingany aqueous dispersion among (1) an aqueous dispersion wherein a matrixmaterial and abrasive are contained and dispersed separately, (2) anaqueous dispersion wherein composite particles are contained anddispersed, (3) an aqueous dispersion wherein composite particles andabrasive are contained and dispersed, (4) an aqueous dispersion whereincomposite particles and a matrix material are contained and dispersed,and (5) an aqueous dispersion wherein composite particles, a matrixmaterial, and abrasive are contained and dispersed.

The above-mentioned “matrix material” is a material comprising a matrixphase that holds the abrasive in the polishing body in the invention,and is comprised of one component or two or more components. Ahomopolymer or a copolymer (rubber, resin, thermoplastic elastomer andthe like) may be used as the matrix material. The matrix material may becrosslinked or uncrosslinked (a crosslinkable material is included.).Examples of the matrix material may include diene-based copolymers,styrene-based copolymers, (meth)acrylic-based resins, acrylic-basedcopolymers, polyolefin-based resins, olefin-based copolymers,epoxy-based resins, phenol-based resins, polyimide-based resins and thelike. Among these, thermoplastic resins such as (meth)acrylic-basedresins, acrylic-based copolymers, polyolefin-based resins, olefin-basedcopolymers and the like are normally used without crosslinking. Also,epoxy-based resins, phenol-based resins, polyimide-based resins,diene-based copolymers and the like prior to curing, are crosslinkableand are uncrosslinked matrix materials. Furthermore, crosslinkedproducts obtained by crosslinking such crosslinkable materials [forexample, cured thermoplastic resins (cured epoxy-based resins, curedphenol-based resins, cured polyimide-based resins), crosslinkeddiene-based copolymers and the like] are crosslinked matrix materials.Any of the matrix material is preferably dispersed in the aqueousdispersion as particles with average particle diameter of 10 μm or less(and more preferably 0.3 to 3 μm).

In particular, the above-mentioned “matrix material” preferably iscomprised of a crosslinkable polymer (including oligomers) and theabove-mentioned polishing part preferably has formed therein acrosslinked structure, in which the crosslinkable polymer iscrosslinked. In this case, the crosslinkable matrix material may bedispersed in the uncrosslinked state in the aqueous dispersion and thematrix material may be crosslinked during the process of solidifying theaqueous dispersion or after solidification of the aqueous dispersion. Inperforming this crosslinking, a crosslinkable oligomer and the like maybe crosslinked without crosslinking agent, or a crosslinking agent maybe blended in the aqueous dispersion to perform crosslinking. In thesecases, crosslinking may be carried out by reaction under roomtemperature or by heating. Also, an uncrosslinked thermoplastic resinmay be crosslinked by irradiation of radiation and the like. Such apolishing part having crosslinking structure gives little surfacedeterioration due to heat during a cutting process. Thus this polishingbody makes processing of a required small distribution of thickness andcutting such as grooving easier without lowering the polishingperformance.

A non-crosslinking component as the matrix material may be used incombination with a crosslinkable component. In this case, the amount ofthe crosslinkable component is 15% by mass or more, more preferably 40%by mass or more with respect to the total amount of the crosslinkablecomponent and the non-crosslinking component. The amount less than 15%by mass of the crosslinkable component makes the effect of restrainingthe deterioration of the surface of the polishing body lower.

In the process of solidifying the aqueous dispersion, if integration byheating and the like is difficult due to the matrix material being acrosslinking polymer, a crosslinking copolymer or the like, the matrixmaterial may be adhered by use of a binder. As this binder, the samecopolymer and/or resin as the above-mentioned matrix material may beused. It is especially preferable to select components wherein theaffinity of the matrix material and the binder is good. Examples of thebinder include epoxy-based resins, phenol-based resins, polyimide-basedresins, styrene-based resins, acrylic-based resins, olefin-based resinsand the like.

The above-mentioned matrix material having crosslinked structure is alsopreferably dispersed in the aqueous dispersion as particles with averageparticle diameter of 10 μm or less (and more preferably 0.3 to 3 μm).

The above-mentioned “abrasive” is a particle that mainly exhibitsmechanical polishing action and/or chemical polishing action. Examplesof such abrasive include particles comprised of cerium oxide, silica,alumina, titanium oxide, chromium oxide, manganese dioxide, dimanganesetrioxide, iron oxide, zirconium oxide, silicon carbide, boron carbide,diamond, barium carbonate and the like. Among these, cerium oxide,silica, alumina and the like, which have good affinity for water, arepreferable. In particular, cerium oxide is more preferable for its gooddispersion property in an emulsion.

The average particle diameter of the above-mentioned abrasive isfavorably 0.001 to 100 μm (preferably 0.005 to 50 μm, more preferably0.005 to 10 μm, and most preferably 0.01 to 1 μm). If the averageparticle diameter is less than 0.001 μm, the polishing effect tends tobe low. Meanwhile, if the average particle diameter is exceeding 100 μm,scratch tends to cause since the abrasive are large. It is alsopreferable for the abrasive to have a particle diameter in thepreferable range given above even in the polishing body.

The above-mentioned “composite particles” are particles wherein theabrasive is attached to the matrix material (the attachment is notlimited to the surface of the matrix material). The attaching method isnot restricted in particular, and for example the abrasive may beattached electrostatically by varying the zeta potential with adjustmentof the pH, etc. In this case, the zeta potentials of the matrix materialand the abrasive are preferably opposite in sign and the potentialdifference is preferably 5 mV or more (more preferably 10 mV or more,even more preferably 20 mV or more and especially preferably 30 mV ormore). For this purpose, a matrix material and the abrasive, which canexhibit the above-mentioned preferable zeta potential signs andpotential difference, should be selected. Also, the zeta potential ofthe matrix material may be made closer to the desired value (a morenegative value) by the introduction of at least one type of group amongthe carboxyl group, sulfonic acid group, amino group, sulfuric estergroup, phosphoric ester group, ether-bonded part, ester-bonded part andthe like. In other words, though most zeta potentials of the matrixmaterial are negative over all pH range or over a wide range except fora low pH range, the matrix material having a carboxyl group, sulfonicacid group and the like may have definitely a negative zeta potential.And, the matrix material having an amino group and the like can be theone having a positive zeta potential within a specific pH range.Meanwhile, the zeta potential of abrasive highly depends on pH, and hasan isoelectric point at which this zeta potential becomes 0, and thesigns of the zeta potential change around this isoelectric point. Thusby choosing a specific matrix material and abrasive, and mixing them ina pH range wherein their zeta potentials will be opposite in sign, thematrix material and the abrasive may be made into composite particleselectrostatically. Also, even if the zeta potentials are the same insign during mixing, by changing the pH thereafter so that the zetapotentials will be opposite in sign, the matrix material and theabrasive may be made integral.

Furthermore, after attaching the abrasive, the composite particlesurface may be covered by a polycondensate of a silane coupling agentand the like preventing from eliminating of the attached abrasive. Thispolycondensate does not necessarily bond chemically to the compositeparticles, and, in particular, a polycondensate that has grownthree-dimensionally may be physically held on the composite particlesurface. Examples of such coated composite particles include onecomposited by bonding polysiloxane and the like at least on the surfaceof the particle after polycondensating a specific silane coupling agentand a specific alkoxysilane, aluminum alkoxide, titanium alkoxide andthe like in the presence of particles that have been made into compositeparticles by electrostatically.

The dispersion medium of the above-mentioned “aqueous dispersion” may bejust a water or a mixed dispersion medium containing other dispersionmedium besides water. In the case of the mixed dispersion medium, thewater content is preferably 10% by mass or more (more preferably 20 mass% or more). Examples of the dispersion medium besides water includenon-protonic polar solvents, esters, ketones, phenols, alcohols, amines,and other dispersion media. The dispersion medium with a boiling pointof 60 to 200° C. (preferably 60 to 160° C.) is used preferably so thatexcessive evaporation will not occur in the preparation of the aqueousdispersion and yet the removal of the dispersion medium can be performedreadily.

The solid content of the aqueous dispersion is preferably 1 to 80% bymass (more preferably 10 to 60% by mass). Exceeding 80% by mass maylower the dispersion stability of the aqueous dispersion andprecipitation may occur.

The aqueous dispersion is preferably one wherein abrasive is dispersedin an emulsion in which the matrix material is dispersed. Dispersingabrasive in the emulsion makes a polishing body with well-dispersedabrasive. The method of dispersing abrasive is not restricted inparticular, and for example, the dispersion may be obtained by mixing anemulsion containing a matrix material which has been prepared byemulsion polymerization, suspension polymerization and the like, and adispersion wherein the abrasive is dispersed. Furthermore, the aqueousdispersion may be obtained by dispersing the abrasive directly in theemulsion.

The method of producing an emulsion in which a matrix material isdispersed is not restricted in particular, for example, the emulsion maybe obtained by emulsion polymerization, suspension polymerization andthe like. The emulsion may also be obtained by dissolving a priorlyobtained matrix material in a solvent or the like, and then dispersingthe resulting solution.

Besides the dispersion medium, matrix material, abrasive and compositeparticles, the aqueous dispersion may contain, as option, a bindermentioned above, a surfactant, a vulcanizing agent, a vulcanizationaccelerator, a crosslinking agent, a crosslinking promotor, a filler, afoaming agent, hollow particles (expanding or non-expanding), which formvoids, a softening agent, an antioxidant, an ultraviolet absorber, anantistatic agent, a plasticizer and the like. An oxidizing agent, ahydroxide of alkali metal, an acid, a pH adjuster, a multivalent metalion (chelating agent), a scratch prevention agent and the like whichhave been conventionally contained in a slurry used in CMP, may also becontained in the aqueous dispersion.

The above-mentioned surfactant may be a cationic surfactant, an anionicsurfactant or a nonionic surfactant. Examples of the cationic surfactantinclude aliphatic amine salts, aliphatic ammonium salts and the like.Examples of the anionic surfactant include fatty acid soaps, carboxylicacid salts such as salts of alkyl ether carboxylic acids,alkylbenzenesulfonates. Examples of the nonionic surfactant includeether type nonionic surfactants such as polyoxyethylene alkyl ethers,ether ester type nonionic surfactants such as polyoxyethylene ether ofglycerin ester, and ester type nonionic surfactants such as polyethyleneglycol fatty acid esters, glycerin ester and sorbitan ester. Thenonionic surfactant is preferable in preventing the scratches occurrenceon the surface effectively.

Examples of the above-mentioned oxidizing agent include organicperoxides such as peracetic acid, perbenzoic acid andtert-butylhydroperoxide, permanganic acid compounds such as potassiumpermanganate, dichromic acid compounds such as potassium dichromate,halogenic acid compounds such as potassium iodate, nitric acid compoundssuch as nitric acid, iron nitrate, perhalogenic acid compounds such asperchloric acid, transition metal salts such as potassium ferricyanide,persulfates, such as ammonium persulfate, heteropolyacids and the like.

Examples of the above-mentioned vulcanizing agent include sulfur (powdersulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, highlydispersible sulfur and the like), sulfur compounds (sulfur monochloride,sulfur dichloride and the like) and the like.

Examples of the above-mentioned crosslinking agent include peroxides(dicumyl peroxide, di-t-butyl peroxide and the like), oximes (p-quinonedioxime, p,p′-dibenzoylquinone dioxime and the like), polyamines(triethylene tetramine, hexamethylenediamine carbamate,4,4′-methylene-bis-o-chloroaniline and the like), modified phenol resins(alkylphenol resins with methylol group and the like) and the like.

An organic acid is preferable as the above-mentioned acid. Examples ofthe organic acid include p-toluenesulfonic acid, dodecylbenzenesulfonicacid, isoprenesulfonic acid, gluconic acid, lactic acid, citric acid,tartaric acid, malic acid, glycolic acid, malonic acid, formic acid,oxalic acid, succinic acid, fumaric acid, maleic acid, phthalic acid andthe like. One type of the organic acid may be used alone or incombination of two or more. An inorganic acid such as nitric acid,hydrochloric acid, sulfuric acid and the like may also be given asexamples of the above-mentioned acid.

Examples of the above-mentioned pH adjuster include inorganic acids suchas hydrochloric acid and sulfuric acid, and basic agents such as sodiumhydroxide and potassium hydroxide.

Examples of the above-mentioned multivalent metal ions include ions ofmetal such as aluminum, titanium, vanadium, chromium, manganese, iron,cobalt, nickel, copper, zinc, germanium, zirconium, molybdenum, tin,antimony, tantalum, tungsten, lead and cerium. One type of suchmultivalent metal ions may be used alone or in combination of two ormore.

Examples of the above-mentioned scratch prevention agent includebiphenol, bipyridyl, 2-vinylpyridine, 4-vinylpyridine, salicylaldoxime,o-phenylenediamine, m-phenylenediamine, catechol, o-aminophenol,thiourea, N-alkyl-group-containing (meth)acrylamide,N-aminoalkyl-group-containing (meth)acrylamide, heterocyclic compounds,which have a penta-heterocyclic ring and does not have askeleton-forming aromatic ring(7-hydroxy-5-methyl-1,3,4-triazainodolizine, etc.), heterocycliccompounds, which have a penta-heterocyclic ring and have askeleton-forming aromatic ring (5-methyl-1H-benzotriazole, etc.),phthalazine, compounds, which have a hexa-heterocyclic ring containingthree nitrogen atoms (melamine, 3-amino-5,6-dimethyl-1,2,4-triazine,etc.), and various derivatives of the compounds given above.7-hydroxy-5-methyl-1,3,4-triazaindolizine is especially preferable asthe scratch prevention agent. A surfactant may also be used as a scratchprevention agent.

The above-mentioned “solidification” normally requires a dispersionmedium elimination (drying) process and a molding process. These twoprocesses may be carried out simultaneously or separately. Or, aftereliminating the dispersion medium to some extent, molding may beperformed and thereafter, complete elimination of the dispersion mediummay be performed. The method maybe selected as suitable in accordancewith the properties of the matrix material and the like. Also, afterelimination of the dispersion medium, a process of crushing the driedproduct further may be provided, and thereafter, the finely crushedpowder may be molded.

The elimination of the dispersion medium may for example be performed byleaving in an open system and eliminating the dispersion mediumnaturally by evaporation. The evaporation of the dispersion medium mayfurthermore be promoted by heating, depressurizing and the like.

The dispersion medium may also be eliminated by the spray drying method.By this method, the dispersion medium can be evaporated rapidly andgranulation can be performed at the same time. This spray drying methodis the one the prescribed aqueous dispersion is made into a fine mistwhich is then ejected into hot air or vacuum to obtain a powdery drypowder (granulated product) instantaneously. Using this spray dryingmethod, the crushing process after the drying process can be omitted,the particle size distribution of the powder can be made narrow anduniform, and as result, the amount filled into a mold in the process ofperforming powder molding can be stabilized and the distribution of theweights of individual molded products can be reduced. Furthermore, sincea granular powder that is more uniformly dispersed than a crushedproduct can be obtained, a molded product of higher strength can beobtained by the use of a powder obtained by spray drying. Furthermore,the denseness distribution of the interior of the polishing body can besmall and the polishing performance for each polishing process can bestabilized.

The above-mentioned molding process can be formed a residue (in the formof lump, flake, powder, pellet and the like) from which the dispersionmedium has been eliminated to some extent, or a dried powder (includinga granular product) from which the dispersion medium has beensubstantially eliminated nearly completely, by performing press molding,extrusion molding, injection molding and the like.

In the case where the elimination of the dispersion medium and moldingare to performed simultaneously, the aqueous dispersion may be chargedinto a desired mold and solidification to the shape of the mold may beperformed by eliminating the dispersion medium in the same manner asdescribed above. Also, without using a mold, the aqueous dispersion maybe developed across the surface of a layer and the like, which is to bethe base material, and thereafter the dispersion medium may beeliminated in the same manner as described above. Various additives,such as those mentioned above, may be added in the molding process.

The above-mentioned “polishing part” exhibits a mechanical and/orchemical polishing effect. The entirety of the polishing body (which forexample is of a plate-like shape and particularly of a disk-like shape)in the invention may be comprised of the polishing part. And thepolishing body may be the one equipped with the polishing part on thesurface of a plate-like body as a supporting part (the shape thereof isnot limited and may be disk-like or square-shaped), or the one whosethin polishing part in predetermined shape is arranged in a regularmanner on the surface of the polishing body. The material of thesupporting part is not particularly restricted and a polyurethane resin(foamed or unfoamed), metal, nonwoven fabric and the like may be used.Among these, a flexible polyurethane resin or a metal (in particular,stainless steel, etc.) is especially preferable.

With the polishing body in the invention, the volume ratio of theabrasive in the polishing body may be 1 to 99% by volume (morepreferably 10 to 70% by volume and especially preferably 15 to 50% byvolume). The polishing body in the invention is preferably used in thepolishing of a semiconductor. Objects to be polished that can bepolished by the polishing body include glass, silicon oxide layer,amorphous silicon layer, polycrystalline silicon layer, monocrystallinesilicon layer, silicon nitride layer, pure tungsten layer, pure aluminumlayer, pure copper layer and the like, as well as layers of an alloy oftungsten, aluminum, copper, and another metal. Objects that can bepolished by this polishing body also include layers of oxides andnitrides of such metals as tantalum, titanium.

PREFERRED EMBODIMENTS OF THE INVENTION

This invention will be described more specifically by way of examplesand comparative examples. However, this invention is not limited tothese examples.

<A > Examples of Use of Thermoplastic Resin as the Matrix Material

[1] Preparation of Non-Crosslinked Type Polishing Bodys

(1) Preparation of Aqueous Dispersions A to C and Non-Aqueous DispersionD

{circle around (1)} Aqueous Dispersion A, Having a Matrix Material andAbrasive Dispersed Therein

The respective components shown in Table 1 were charged at therespective proportions into a temperature-adjustable autoclave, equippedwith a stirrer, and were reacted for 16 hours at 75° C. As a result, thepolymerization conversion was 95.8% and an aqueous thermoplastic resinemulsion was obtained in which a copolymer (thermoplastic resin), with aglass transition temperature of 50° C. and an average particle diameterof 166 nm, was dispersed. The particle diameter was measured using alaser particle size analysis system made by Otsuka Electronics Co., Ltd.(in the description that follows, the particle diameter was measured bythe same method).

TABLE 1 Component Amount (parts) Ion-exchanged water 240 Butadiene 14.00Styrene 71.00 Methylene methacrylate 12.15 Itaconic acid 1.85 Acrylicacid 1.00 á-Methylstyrene dimer 0.10 t-Dodecylmercaptan 0.40

The emulsion that was obtained as described above was adjusted to pH8.5by means of a 25% aqueous solution of potassium hydroxide. Thereafter,water (ion-exchanged water) was added and stirring was performed underroom temperature using a “Three-One Motor.” After incorporating a ceriumoxide (CeO₂) powder with a particle diameter of 0.3 μm prior toprocessing, stirring at 1,500 rotations/minute was carried out for 3minutes to obtain an aqueous dispersion A.

{circle around (2)} Aqueous Dispersion B, Having Composite ParticlesWherein Abrasive is Attached to a Matrix Material Dispersed

The respective components shown in Table 2 were charged at therespective proportions into a flask of 2-liter volume and were made toundergo polymerization under a nitrogen atmosphere by stirring at 70° C.for 6 hours. An emulsion, containing polymethyl methacrylate polymerparticles, having an amino group of a cationic functional group, and afunctional group with a polyethylene glycol chain, was thereby obtained.The polymerization yield was 95%.

The product of the trade name, “NK Ester M-90G #400”, made byShin-Nakamura Chemical Co., Ltd., was used as the methoxypolyethyleneglycol methacrylate in Table 2, and the product of the trade name,“V50”, made by Wako Pure Chemicals Industries, Ltd., was used as theazo-based initiator.

TABLE 2 Component Amount (parts) Ion-exchanged water 400 Methylmethacrylate 90.00 Methoxypolyethylene glycol 5.00 methacrylate4-Vinylpyridine 5.00 Azo-based initiator 2.00

The obtained emulsion containing 10% by mass of polymethyl methacrylatepolymer particles, was then adjusted to pH10 by means of potassiumhydroxide. The zeta potential of the polymethyl methacrylate polymerparticles in this emulsion was +17 mV. Meanwhile, the dispersion, whichwas prepared to contain 10% by mass of a cerium oxide powder with aparticle diameter of 0.3 μm prior to processing, was adjusted likewiseto pH10. The zeta potential of the cerium oxide in this dispersion was−18 mV. The difference of the zeta potentials of the two components wasthus 35 mV.

Thereafter, the above emulsion and dispersion were charged at a massratio of 1:1 into a flask of 2-liter volume and then mixed by stirring.3 parts by mass of tetraethoxysilane were then added into the flask andthen stirring for 1 hour at 25° C., followed by stirring for 3 hours at40° C., was performed. The mixture was then cooled to obtain an aqueousdispersion B wherein composite particles were dispersed. Cerium oxidewas attached to 95% of the surface of these composite particles.

{circle around (3)} Aqueous Dispersion C, Having Composite ParticlesWherein Abrasive is Attached to a Matrix Material Dispersed

The respective components shown in Table 3 were charged at therespective proportions into a flask of 2-liter volume and were made toundergo polymerization under a nitrogen atmosphere by stirring at 70° C.for 6 hours. An emulsion, containing carboxy-modified polystyreneparticles, having a carboxyl group and a hydroxyl group, was therebyobtained. The polymerization yield was 95%, and the carboxyl groupcontent as measured by the conductometric titration method was 40% forthe carboxy-modified polystyrene particle interior, 50% for the surface,and 10% for the aqueous phase part.

TABLE 3 Component Amount (parts) Ion-exchanged water 400 Styrene 92.00Methacrylic acid 4.00 Hydroxyethyl acrylate 4.00 Ammonium lauryl sulfate0.10 Ammonium persulfate 0.50

The obtained emulsion containing 10% by mass of carboxy-modifiedpolystyrene particles, was then adjusted to pH4 by means of nitric acid.The zeta potential of the carboxy-modified polystyrene particles in thisemulsion was −40 mV. Meanwhile, the dispersion, which was prepared tocontain 10% by mass of cerium oxide powder with an average particlediameter of 0.3 μm prior to processing, was adjusted likewise to pH4.The zeta potential of the cerium oxide in this dispersion was +20 mV.The difference of the zeta potentials of the two components was thus 60mV.

Thereafter, the above emulsion and dispersion were charged at a massratio of 1:1 into a flask of 2-liter volume and then mixed by stirring.3 parts by mass of tetraethoxysilane was then added into the flask andthen stirring for 1 hour at 25° C., followed by stirring for 3 hours at40° C., was performed. The mixture was then cooled to obtain an aqueousdispersion C wherein composite particles were dispersed. Cerium oxidewas attached to 90% of the surface of these composite particles.

{circle around (4)} Non-Aqueous Dispersion D, Having a Matrix Materialand Abrasive Dispersed Therein

The aqueous dispersion medium of an emulsion obtained in the same manneras in {circle around (1)} was evaporated and dried. Thereafter, the sameamount of toluene as the amount of the evaporated and dried aqueousdispersion medium was added and mixing by stirring was performed. Thesame amount of cerium oxide powder as that used in {circle around (1)}was mixed by stirring into the liquid to thereby obtain non-aqueousdispersion D. As cerium oxide was added, the viscosity of the dispersionincreased and it became impossible to continue stirring during theprocess.

(2) Molding

Each of the aqueous dispersions A to C and non-aqueous dispersion Dobtained in (1) was spread thinly across a polyethylene film and madeflake-like in form by leaving and drying for 48 hours under roomtemperature. Each flake-like product thus obtained was then formed usinga mold press to thereby obtain disk-shaped polishing bodys A to D of 30cm diameter and 3 mm thickness. The polishing bodys A to C are in theinvention while polishing body D is a comparative example.

[2] Evaluation of the Dispersion Property of the Abrasive and Evaluationof the Polishing Bodys A to D

(1) Evaluation of the Dispersion Property of the Abrasive

For each of the aqueous dispersions A to D, the dispersion medium waseliminated, the resulting residue was magnified by a transmissionelectron microscope, and the maximum diameters of 50 abrasive weremeasured respectively using the electron microscope photograph that wastaken, and the average maximum diameter was calculated as the averagevalue of the measured values. The results are shown in Table 4.

(2) Evaluation of Polishing Performance

{circle around (1)} Measurement of Removal Rate

Each of the polishing bodys A to D was adhered onto the surface table ofa polishing device (model “LM-15,” made by Lapmaster STF Corp.) and a 4cm-square thermally oxidized layer wafer was polished while supplyingjust water at a rate of 150 cc per minute. The other polishingconditions were; a table rotation speed of 50 rpm, head rotation speedof 50 rpm, polishing pressure of 350 g/cm², and polishing time of 2minutes. The removal rate was then calculated from the results by usingthe following formula (1).Removal rate(Å/minute)=(Thickness of oxide layer beforepolishing−Thickness of oxide layer after polishing)/Polishing time  (1){circle around (2)} Evaluation of Scratching

The surfaces of wafers polished in {circle around (1)} were observedvisually and evaluated. The results are shown in Table 4. In Table 4,“None” indicates that no scratches whatsoever could be found by visualobservation. “Numerous” indicates that numerous scratches were observedby visual observation.

TABLE 4 Polishing Polishing Polishing Polishing body D body A body Bbody C (Comparative (Example) (Example) (Example) example) Primaryparticle 0.3 diameter (μm) Secondary particle 0.3 0.3 0.4 2.0 diameter(μm) Removal rate 2,000 1,800 1,700 1,800 (Å/minute) Scratches None NoneNone Numerous

According to the results in Table 4, whereas the particle diameter ofthe abrasive prior to processing was 0.3 μm, the particle diameterbecame 0.3 to 0.4 μm in the condition immediately prior to forming intothe polishing body. That is, the particle diameter became 1 to 1.3 timesthe average particle diameter and it is thus predicted that the abrasivewas contained in the polishing body without changing in particlediameter from that prior to processing. Meanwhile, whereas the particlediameter prior to processing was 0.3 μm in regard to the polishing bodyD, which is not of the invention, the particle diameter became 2.0 μm inthe condition immediately prior to forming into the polishing body. Thatis, the particle diameter increased by 7.3 times the average particlediameter and it is thus predicted that the abrasive was largelyaggregated in the polishing body D as well. Also, whereas visuallyrecognizable scratches were not seen on the wafers polished by thepolishing bodys of the polishing bodys A to C, numerous scratches wereseen on the wafer polished by the polishing body D.

<B > Examples of Use of Thermosetting Resin as the Matrix Material

[1] Preparation of Crosslinked Type Polishing Bodys

(1) Preparation of Aqueous Dispersions E to G

(a) Aqueous Thermosetting Resin a

The aqueous epoxy resin “EM101-50,” made by Asahi Denka Kogyo K.K.(solid content; 50% by mass), was used.

(b) Aqueous Thermoplastic Resin b

The aqueous thermoplastic resin emulsion (solid content; 48% by mass)described above, was used.

{circle around (1)} Aqueous Dispersion E, Having a ThermosettingResin-Based Matrix Material and Abrasive Dispersed Therein

The aqueous thermosetting resin a was adjusted to pH8.5 by means of a25% aqueous solution of potassium hydroxide. Water (ion-exchanged water)was then added and stirring was performed at room temperature using a“Three-One Motor.” After incorporating a cerium oxide (CeO₂) powder witha particle diameter of 0.3 μm prior to processing, the curing agent“EH-3615S” was incorporated and stirring at 600 rotations/minute wascarried out for 3 minutes to obtain an aqueous dispersion E.

{circle around (2)} Aqueous Dispersion F, Having Dispersed Therein aMatrix Material, in which a Thermosetting Resin-Based is Combined with aThermoplastic Resin-Based, and Abrasive

The aqueous thermoplastic resin b and water (ion-exchanged water) wereadded to aqueous thermosetting resin a and stirring at room temperaturewas performed. The proportions of the solid content of the aqueousthermosetting resin a and the aqueous thermoplastic resin b were set sothat the aqueous thermosetting resin a will comprise 50% by mass basedon the total of both resins.

The dispersion was then adjusted to pH8.5 by means of a 25% aqueoussolution of potassium hydroxide. After then incorporating a cerium oxide(CeO₂) powder with a particle diameter of 0.3 μm prior to processing,the above-mentioned curing agent “EH-3615S” was incorporated andstirring at 600 rotations/minute was carried out for 3 minutes to obtainan aqueous dispersion F.

{circle around (3)} Aqueous Dispersion G, Having a Thermoplastic Resinand Abrasive Dispersed Therein

Water (ion-exchanged water) was added to aqueous thermoplastic resin band stirring was performed at room temperature. The dispersion was thenadjusted to pH8.5 by means of a 25% aqueous solution of potassiumhydroxide. After then incorporating a cerium oxide (CeO₂) powder with aparticle diameter of 0.3 μm prior to processing, the above-mentionedcuring agent “EH-3615S” was incorporated and stirring at 600rotations/minute was carried out for 3 minutes to obtain an aqueousdispersion G.

(2) Molding

Each of the aqueous dispersions E to G obtained in (1) was spread thinlyacross a polyethylene film and made flake-like products in form byleaving and drying for 48 hours under room temperature. Each flake-likeproduct thus obtained was then formed using a mold press to therebyobtain disk-shaped polishing bodys E to G of 30 cm diameter and 3 mmthickness. Polishing bodys E and F are in the invention (examples) whilepolishing body G is a comparative example.

[2] Evaluation of Machinability and Evaluation of Polishing Bodys E to G

(1) Cutting

Cutting of the surface was carried out in order to increase the surfaceprecision of each of the polishing bodys of 30 cm diameter and 3 mmthickness. A machining center was used for cutting and an end mill wasused as the cutting tool. The cutting amount was set to 0.02 mm and thefeeding speed was set to 100 mm/minute.

(2) Evaluation of Machinability

The machinability was evaluated by comparison of the removal rate beforeand after cutting. Each of the polishing bodys A to C was adhered ontothe surface table of a polishing device (model “LM-15,” made byLapmaster STF Corp.) and a 4 cm-square thermally oxidized layer waferwas polished while supplying just water at a rate of 150 cc per minute.The other polishing conditions were a table rotation speed of 50 rpm,head rotation speed of 50 rpm, polishing pressure of 350 g/cm², andpolishing time of 2 minutes. The dressing conditions were; a dressernumber of #100, table rotation speed of 30 rpm, head rotation speed of30 rpm, dressing pressure of 300 g/cm², and dressing time of 10 minutes.The removal rate was then calculated from the results by using thefollowing formula (1).Removal rate(Å/minute)=(Thickness of oxide layer beforepolishing−Thickness of oxide layer after polishing)/Polishing time  (1)The polishing results are shown in Table 5.

TABLE 5 Polishing body F Polishing body E (thermosetting resin +Polishing body G (thermosetting resin) thermoplastic resin)(thermoplastic resin) Units Uncut Cut Uncut Cut Uncut Cut Distributionof 110 25 100 20 100 20 thickness (maximum) Removal rate; Å/minute 1,1001,300 1,000 1,300 1,000 250 without dressing Removal rate; Å/minute1,100 1,500 1,000 1,500 1,000 25 with dressing

According to the results in Table 5, the distribution of thickness ofthe polishing body as a whole were small as intended for all polishingbodys E to G. With regard to the removal rate, those of the cuttingproducts of polishing bodys E and F was large in comparison to those ofthe uncutting products, but the removal rate of the cutting productusing the polishing body G became considerably low. This is because withpolishing bodys E and F, the distribution of the thickness was made lowby cutting. On the other hand, with the comparative example polishingbody G, though the distribution of thickness was made low, it isconsidered that surface of the polishing body melted slightly due to theheat during cutting and the surface thus became deteriorated somewhat.In contrast, deterioration of the surface was not seen with thepolishing bodys E and F of the invention.

<C> Example of Employment of the Spray Drying Method

Using the aqueous dispersion A described above, the spray drying methodwas carried out under the following operation conditions to obtaingranular particles of an average particle diameter of 60 μm.

[Spray Drying Method Conditions]

Equipment used; “OC-16”; made by Ohkawara Kakohki Co., Ltd., sprayingdisk diameter; 65 mm, inlet temperature; 160° C., outlet temperature;65° C., spraying disk rotation speed; 15,000 rpm, stock solutiontreatment rate; 12 kg/h.

This dried powder was then molded using a powder press to obtain apolishing body H.

As a result of testing the flexural strength of the polishing body H bythe method described below, it was found that whereas the flexuralstrength of the polishing body E, measured in the same manner, was 130kgf/cm², that of the polishing body H was 330 kgf/cm². This comparisonof the two polishing bodys shows that the polishing body H excels interms of flexural strength.

[Test Method]

A test in compliance with ASTM 638 was performed using the InstronUniversal Material Tester 4204.

1. A polishing body, comprising: a polishing part with a predeterminedshape molded from a residue or a dried powder; said residue or driedpowder being prepared by eliminating a dispersion medium from an aqueousdispersion comprising dispersed composite particles comprising anabrasive attached to a matrix material, said abrasive being dispersed insaid matrix material, wherein the respective zeta potentials of saidmatrix material and said abrasive are opposite in sign and thedifference of said zeta potentials is 5 mV or more.
 2. The polishingbody according to claim 1, wherein said dispersion medium is eliminatedby spray drying.
 3. The polishing body according to claim 1, whereinsaid aqueous dispersion further comprises a matrix material and/or anabrasive.
 4. The polishing body according to claim 1, wherein thepolishing body is adapted for the polishing of semiconductors.
 5. Apolishing body, comprising: a polishing part with a predetermined shapemolded from a residue or a dried powder; said residue or dried powderbeing prepared by eliminating a dispersion medium from an aqueousdispersion comprising dispersed composite particles comprising anabrasive attached to a matrix material, said matrix material comprisinga crosslinkable polymer, said crosslinkable polymer being crosslinkedduring elimination of said dispersion medium, or during molding, orafter molding, thereby obtaining a crosslinked structure, and saidabrasive being dispersed in said matrix material, wherein the respectivezeta potentials of said matrix material and said abrasive are oppositein sign and the difference of said zeta potentials is 5 mV or more. 6.The polishing body according to claim 5, wherein said dispersion mediumis eliminated by spray drying.
 7. The polishing body according to claim5, wherein the polishing body is adapted for the polishing ofsemiconductors.
 8. A polishing pad, which comprises the polishing bodyaccording to claim
 1. 9. A polishing pad, which comprises the polishingbody according to claim
 5. 10. A method for polishing of semiconductors,comprising: polishing a semiconductor with the polishing body accordingto claim
 1. 11. A method for polishing of semiconductors, comprising:polishing a semiconductor with the polishing body according to claim 5.12. A polishing body, comprising: a polishing part with a predeterminedshape molded from a residue or a dried powder; said residue or driedpowder being prepared by eliminating a dispersion medium from an aqueousdispersion comprising dispersed composite particles comprising anabrasive attached to a matrix material wherein the respective zetapotentials of said matrix material and said abrasive are opposite insign and the difference of said zeta potentials is 5 mV or more.
 13. Thepolishing body according to claim 12, wherein said dispersion medium iseliminated by spray drying.
 14. The polishing body according to claim12, wherein said aqueous dispersion further comprises a matrix materialand/or an abrasive.
 15. The polishing body according to claim 12,wherein the polishing body is adapted for the polishing ofsemiconductors.
 16. A polishing body, comprising: a polishing part witha predetermined shape molded from a residue or a dried powder; saidresidue or dried powder being prepared by eliminating a dispersionmedium from an aqueous dispersion containing dispersed compositeparticles comprising an abrasive attached to a matrix material, saidmatrix material comprising a crosslinkable polymer, said crosslinkablepolymer being crosslinked during elimination of said dispersion medium,or during molding, or after molding, thereby obtaining a crosslinkedstructure, wherein the respective zeta potentials of said matrixmaterial and said abrasive are opposite in sign and the difference ofsaid zeta potentials is 5 mV or more.
 17. The polishing body accordingto claim 16, wherein said dispersion medium is eliminated by spraydrying.
 18. The polishing body according to claim 16, wherein thepolishing body is adapted for the polishing of semiconductors.
 19. Apolishing pad, which comprises the polishing body according to claim 12.20. A polishing pad, which comprises the polishing body according toclaim
 16. 21. A method for polishing of semiconductors, comprising:polishing a semiconductor with the polishing body according to claim 12.22. A method for polishing of semiconductors, comprising: polishing asemiconductor with the polishing body according to claim 16.